This invention relates to weatherable compositions, and more particularly to weatherable coating compositions for application to thermoplastic substrates.
It has long been conventional to apply protective coating compositions to abrasion-susceptible substrates such as polycarbonates and poly(methyl methacrylate) in sheet form, to improve their resistance to degradation of various kinds, including abrasion and degradation. Among the coating compositions employed for this purpose are those derived from a polymeric polyol, sometimes in combination with a low molecular weight diol, and an aminoplast.
Polymeric articles thus coated frequently have a problem of long term color instability. This causes yellowing of the polymeric substrate, detracting from its transparency and attractiveness. Loss of gloss can also be an undesirable long term phenomenon.
Yellowing of polymers is often caused by the action of ultraviolet radiation, which is why such yellowing is frequently designated xe2x80x9cphotoyellowingxe2x80x9d. It is particularly vexing when the polymeric article is to be used outdoors, in direct exposure to sunlight.
Numerous means for suppressing photoyellowing have been employed and proposed. Many of these involve incorporating in the coating composition an ultraviolet absorbing compound (UVA). Among the commercially available UVA""s of particular interest are hydroxybenzophenones, hydroxyphenylbenzotriazoles, hydroxyphenyltriazines, cyanoacrylates and polyaroylresorcinols. It is frequently found, however, that these UVA""s do not provide adequate protection against weathering.
A class of UVA""s which has been found particularly useful in many environments for protection against weathering in outdoor exposure situations, is the silylated diaroylresorcinols disclosed in U.S. Pat. Nos. 5,391,795, 5,679,820 and 5,990,188. They are disclosed as being useful in and compatible with silicone hardcoat compositions and silicon-containing ultraviolet-cured coating compositions comprising acrylic monomers. Their use in polyol-aminoplast coating compositions is, however, not disclosed.
It is of interest, therefore, to develop protective coating compositions capable of improved protection of a substrate against weathering as evidenced by photoyellowing and the like.
The present invention is based on the discovery that silylated diaroylresorcinols are particularly effective as WVA""s in polyol-aminoplast protective coating compositions, especially in combination with hindered amine light stabilizers (HALS).
In one of its aspects, the invention includes thermally curable compositions comprising the following and any uncured reaction products thereof:
(A) at least one polymeric polyol,
(B) at least one alkanediol,
(C) at least one reactive aminoplast and
(D) at least one silylated substituted resorcinol of the formula 
wherein:
each A is independently an unsubstituted or substituted aromatic radical,
R1 is a divalent C1-10 aliphatic hydrocarbon radical,
each R2 and R3 is independently a C1-12 alkyl radical, and
n is 0-3.
In another aspect of the invention, said thermally curable compositions further contain at least one hindered amine light stabilizer.
Another aspect of the invention is a method for producing a cured coating on a thermoplastic substrate which comprises:
(I) coating said substrate with a thermally curable composition prepared by blending the constituents described above, and
(II) heating the coated substrate thus formed at a temperature effective to thermally cure said composition.
Still another aspect of the invention is coated resinous articles prepared by the above-described method.
It is immaterial from the standpoint of the invention, and not entirely certain in any event, whether any chemical reaction takes place between the various components as defined hereinafter, with the proviso that no curing reaction has taken place at the time the curable compositions are employed as coatings. Thus, the invention includes simple physical mixtures of said components and also uncured reaction products thereof.
Component A in the compositions of the invention is at least one polymeric polyol. By xe2x80x9cpolymeric polyolxe2x80x9d is meant a polymer, usually of low to medium molecular weight (e.g., a number average molecular weight in the range of about 200-5,000), containing two or more hydroxy groups. For the most part, two hydroxy groups are present as end groups.
Various types of polymeric polyols are known in the art, and any of them may be used in the invention. Illustrations are polyether-, polyester-, polycarbonate- and polyurethane-polyols as well as the polycaprolactone-polyols disclosed in the aforementioned U.S. Pat. No.4,552,936. The polyester-polyols are often preferred by reason of their particular suitability and relatively low cost. They may be illustrated by the xe2x80x9cRUCOFLEXxe2x80x9d hydroxy-terminated polyesters of Ruco Chemical Company, which are generally prepared by the reaction of at least one aliphatic diol, or mixture thereof with at least one triol and/or polyhydroxy compound of higher functionality, with at least one aliphatic and/or aromatic dicarboxylic acid or functional derivative thereof. Examples of diols are ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol; higher polyols include 1,1,1-tris(hydroxymethyl)propane and glycerol. Examples of dicarboxylic acids are adipic acid, succinic anhydride, 1,12-dodecanedioic acid, phthalic anhydride, isophthalic acid and terephthalic acid. Most preferred in many instances are polyester-polyols prepared from adipic acid and a mixture of 1,6-hexanediol and 2,2-dimethyl-1,3-propanediol, as illustrated by the product sold under the trade name xe2x80x9cRUCOFLEX S-1015xe2x80x9d.
Component B is at least one alkanediol, preferably containing about 1-6 carbon atoms. Illustrative alkanediols are ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 2,2-dimethyl-1,3-propanediol. 1,4-Butanediol is usually preferred.
Component C is at least one reactive aminoplast. As used herein, the term xe2x80x9caminoplastxe2x80x9d means a thermosetting amine-aldehyde or amide-aldehyde condensation product, which may be monomeric or polymeric. Exemplary of the aminoplast compositions that may be employed are the urea formaldehydes, e.g., propylene urea formaldehyde and dimethylol urea formaldehyde; melamine formaldehydes, e.g., tetramethylolmelamine, pentamethylolmelamine and hexamethylolmelamine; ethylene ureas, e.g., dimethylol ethylene urea, dihydroxydimethylol ethylene urea, ethylene urea formaldehyde and hydroxyethylene urea formaldehyde; carbamates, e.g., alkyl carbamate formaldehydes; formaldehyde-acrolein condensation products; formaldehyde-acetone condensation products; alkylolamides, e.g., N-methylolformamide, N-methylolacetamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methylol-N-methylacrylamide and N-methylol methylene bis(acrylamide); haloethyleneacrylamide; diureas, e.g., trimethylol acetylene diurea and tetramethylol acetylene diurea; triazones, e.g., dimethylol-N-ethyl triazone, N,Nxe2x80x2-thylenebis(dimethylol)triazone and halo triazones; haloacetamides, e.g. N-methylol-N-methylchloroacetamide; and urons, e.g., dimethylol uron and dihydroxy dimethylol uron. Also useful, and often preferred, are derivatives of the above compounds wherein the methylol or other hydroxyalkyl groups therein are replaced by lower alkoxyalkyl groups (e.g., hexamethoxymethylmelamine), as well as analogous thioureas, thioamides and the like. Particularly preferred are the melamine derivatives and especially hexamethoxymethylmelamine, which is commercially available from Cytec Industries under the trade name xe2x80x9cCYMEL 301xe2x80x9d.
Component D, the silylated substituted resorcinol, has formula I in which the A value may be any unsubstituted or substituted aromatic radical, illustrations being phenyl, p-chlorophenyl, p-tolyl, 1-naphthyl and 2-naphthyl; phenyl is generally preferred. The R1 radical may be, for example, ethylene, trimethylene, tetramethylene, propylene or neopentylene; trimethylene is preferred. The value of n may be from 0 to 3 and is usually 0. Both R2 and R3 may be, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 1-pentyl, 1-octyl, 2-ethylhexyl, 1-decyl or 1-dodecyl, with methyl and ethyl generally being preferred. Preferred compounds of formula I are 2-(3-trialkoxysilylalkyl)-4,6-diaroylresorcinols. The most preferred compound of formula I is 2-(3-triethoxysilylpropyl)-4,6-dibenzoylresorcinol.
The compositions of this invention may contain additional constituents including solvents, curing catalysts, stabilizers, flow modifiers and surfactants. The purpose of the solvent is to facilitate blending and application of the coating composition. Catalysts accelerate curing, and stabilizers serve to reduce activity of the catalysts during storage and before curing is desired.
Suitable solvents include alcohols, ketones, esters, ethers, alkoxy alkanols, halogenated compounds, carboxylic acids and aromatic compounds. They may be used singly or in combination. Particularly suitable solvents are lower alkanols (e.g. methanol, ethanol, propanol and butanol) and alkoxyalkanols as illustrated by ethylene glycol ethers such as the monomethyl, monoethyl and mono-n-butyl ethers, the latter being preferred.
Catalysts include alkyl acid phosphates such as methyl dihydrogen phosphate, ethyl dihydrogen phosphate, propyl dihydrogen phosphate, n-butyl dihydrogen phosphate and di-n-butyl monohydrogen phosphate; phosphoric acid; dicarboxylic acids and their functional derivatives such as maleic acid and anhydride, fumaric acid and chloromaleic acid and anhydride; alkyl hydrogen phthalates such as methyl, ethyl, propyl and butyl hydrogen phthalate; monoalkyl succinates and maleates such as methyl, ethyl, propyl and butyl hydrogen succinates and maleates; and the sulfonic acids and derivatives thereof including p-toluenesulfonic acid and methanesulfonic acid. p-Toluenesulfonic acid is often preferred.
Coating compositions which are to be prepared in advance of or stored prior to application and cure require stabilizers to deactivate the catalyst until cure. It is within the skill of the art to determine suitable stabilizers for use with a given catalyst. For the catalysts previously mentioned including the preferred p-toluenesulfonic acid, amines such as methylaminoethanol, triethylamine and 2-amino-2-methyl-1-propanol may be employed, with triethylamine often being preferred.
It is also often preferred to incorporate a hindered amine light stabilizer (HALS) in the compositions of the invention, since the presence of a HALS can decrease the hazing tendency of said compositions. HALS compounds are known in the art and are generally derivatives of 2,2,6,6-tetramethylpiperidines. Examples are 4-methacryloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloxy-2,2,6,6-tetramethyl-N-methylpiperidine, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidino)-2,5-pyrrolidinedione, 3-dodecyl-1-(2,2,6,6-tetramethyl-N-methyl-4-piperidino)-2,5-pyrrolidinedione, 3-dodecyl-1-(2,2,6,6-tetramethyl-N-acetyl-4-piperidino)-2,5-pyrrolidinedione, copolymers of 4-methacryloxy-2,2,6,6-tetramethylpiperidine with methyl methacrylate, homopolymers of 4-methacryloxy-2,2,6,6-tetramethylpiperidine, and the compound having the formula 
Flow modifying additives useful in the compositions of the invention include cellulose esters. Surfactants include various art-recognized silicone compounds.
Weight ratios of component B to component A in the compositions of the invention are most often in the range of about 0.2-1.0:1 and preferably about 0.5-0.9:1. The weight ratio of component C to component A in the range of about 0.5-2.5:1, and preferably about 0.8-1.4:1. Component D and the HALS, when employed, are present in amounts effective to afford protection against ultraviolet degradation, most often about 1-12 parts and preferably about 4-9 parts (by weight) of component D and about 0.1-2.0 parts and preferably about 0.5-1.5 parts of HALS per 100 parts of non-volatile constituents (phr). Other constituents, including catalysts, stabilizers, flow modifiers and surfactants, may be present in minor proportions known to those skilled in the art. Solvent is usually incorporated in an amount to provide a non-volatiles content (i.e., a content of all constituents except solvent) in the range of about 15-80% by weight.
The coating compositions of the invention may be prepared by simply blending the constituents thereof, typically at temperatures in the range of about 10-35xc2x0 C. They may be applied to substrates by any art-recognized coating method, including brushing, spraying, flow coating, dip coating, drawing down and coextrusion. Following application of the coating composition, any solvent present therein is removed and curing is effected by heating, typically in contact with air and to a temperature in the range of about 100-150xc2x0 C.
The substrates present in the coated articles of this invention are often preferably sheet materials and may be of any suitable thermoplastic material. Examples are polycarbonates, polyesters, polyamides, polyimides and addition polymers including acrylic polymers and polystyrenes (e.g., acrylonitrile-styrene, acrylonitrile-butadiene-styrene and acrylonitrile-styrene-alkyl acrylate copolymers), polyvinyl chloride, polyethylene and polypropylene. Polycarbonates are often preferred, with bisphenol A polycarbonates being most preferred; i.e., polycarbonates derived from 2,2-bis(4-hydroxyphenyl)propane (xe2x80x9cbisphenol Axe2x80x9d).